Hydrocarbons

Vidyamandir Classes Hydrocarbons
Hydrocarbons
Hydrocarbons
ALKANES Section - 1
Hydrocarbons are the binary compounds of carbon and hydrogen only. Hydrocarbons occur in nature in
the form of coal, natural gas and petroleum. All the organic compounds (other than hydrocarbons) are
derived from hydrocarbons, by substituting hydrogen with a functional group or by adding a functional
group. Hydrocarbons are classified into two categories: Aliphatic hydrocarbons (open chains) and Cyclic
hydrocarbons (closed chains). Here, we will first study aliphatic type, which are further divided into Saturated
hydrocarbons (Alkanes) and Unsaturated hydrocarbons (Alkenes, Alkynes), and then cyclic hydrocarbons,
which are further divided into Cycloalkanes, Cycloalkenes and Aromatic Hydrocarbons.
ALKANES : [CnH2n + 2]
Alkanes form a homologous series, represented by a general formula : CnH2n+2. These have a tetrahedral
structure around carbon atom or one can say that all the carbon atoms in alkanes show sp3 type of
hybridisation. The important members of alkanes are: Methane (CH4), Ethane (CH3CH3), Propane
 CH3  C H  CH3 
(CH3CH2CH3), n-Butane (CH3CH2CH2CH3) and its isomer, Iso-butane  | .
 CH3 
 
Generally, alkanes are also represented as : RH, RCH3, R-R, R-R (where R and R are alkyl radical)
Preparation of Alkanes :
1. Reduction of Alkenes and Alkynes :
H
2 C H
Cn H 2n  n 2n  2
Ni/573 K
Alkane
2 2H
Cn H 2n  2  Cn H 2n  2
Pt or Ni/573 K
Alkane
This is known as Sabatatier-Sandern’s reaction.
Note : For the reduction of alkenes, and alkynes Pd – carbon/Ethanol at 25°C (50 atm) is generally used.
Pd  C/C H OH
2 5  CH
 CH3 2  C  CH 2 
  3 2 CHCH3
25 C, 50 atm
Isobutane
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Hydrocarbons Vidyamandir Classes
2. From Alkyl Halides :

(a) By reducing Alkyl Halides :
Reducing agents : Zn + CH3COOH ; Zn + HCl ; Zn + NaOH ; ZnCu Couple ; Al  Hg amalgam.
RX + H2 
 RH + HX
Alkyl iodides are reduced by HI in red P under high temperature and pressure.
Re d P
RI + HI 

 RH + I2 (I2 is removed by P as : 2P + 3I2  
 2Pl3)
150 C, high pressure
(b) Wurtz Reaction :

It involves the condensation of two molecules of alkyl halide with Na and dry ether, to give sym-
metric alkanes
dry
2RI + Na   R – R + NaI
ether
If we start with RI and RI, we get mixture of alkanes. Hence it is not good method for unsymmetric
alkanes.
Note : Methane cannot be formed by this method.
Order of reactivity of alkyl halides RI > RBr > RCl > RF.
(c) Frankland Reaction :

RI + Zn + RI 
 R – R+ ZnI2
3. Reduction of Alcohols :
Re d P
ROH  2HI  RH  I2  H 2O
150C, high Pressure
4. Reduction of Aldehyde and Ketones :

Zn  Hg NH 2 NH 2
RCHO  2H 2   RCH3  H 2O RCH RCH3 + H 2O
HCl alc. KOH
Zn  Hg NH 2 NH 2
RCOR  2H 2   RCH 2 R  H 2O RCOR RCH 2 R + H 2O
HCl alc. KOH
This is known as Clemmensen’s Reduction. This know as Woff-Kishner’s Reduction.
5. From Carboxylic Acids :

(a) Reduction :
Re d P
RCOOH  6HI RCH3  2H 2O  3I2
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(b) Decarboxylation :
It is obtained by heating sodium salts of carboxylic acids with sodalime (NaOH - CaO).
CaO
RCOONa  NaOH  RH  Na 2CO3

Note : In the product there is one carbon less than parent compound. So this reaction is an important method to
reduce a carbon atom in organic synthesis (known as Step-down method).
(c) Kolbe’s Electrolysis :

electrolysis
2CH3COONa  2H 2O 
 CH3  CH3  2CO 2  2NaOH  H2
 
(At Anode) (At Cathode)
6. From Grignard Reagent ( Alkyl magnesium halides, RMgX) :
Note : Any copound having acidic H atom(s), decomposes Grignard reagent.
7. By action of water on Aluminium and Beryllium Carbide :
 3CH 4  4Al  OH 3
Al4C3  12 H 2O 
 CH 4  2 Be  OH 2
Be 2C  4 H 2O 
Note : Only Methane is formed by this reaction.
8. Through formation of Lithium Dialkycuprates :

diethyl
RX  2Li  RLi  LiX
ether
2RLi  CuI 
 R 2CuLi  LiI
Lithium diakyl
cuprate
 Gilman 's Reagent 
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Section 11 3
R 2CuLi  R 'X 
 R  R '  RCu  LiX
This is known as Corey House Synthesis
Note : (i) R can be 1°, 2°, 3° alkyl or aromatic group.

(ii) R should be 1° alkyl or 2° cycloalkyl group or even aromatic group.
Physical Properties of Alkanes :

The physical properties of alkanes such as boiling point, density and solubility depend upon the intermolecular
forces of attraction. The magnitude of these forces of attraction depend upon the surface area of contact
between adjacent molecules. Greater the surfae area, stronger are the forces of attraction.
1. Physical State : The normal alkanes C1 to C4 are colourless gases, C5 to C17 are colourless liquids and
from C18 onwards are colourless waxy solids.
2. Boiling Point : The boiling points of the unbranched alkanes show a regular increase with increasing
molecular weight. The increase is by 20 – 30°C for each –CH2 unit added to the chain. Branching of the
alkane chain, however, lowers the boiling point.
CH3
CH3 |
CH3CH2CH2CH2 -CH3 | CH 3  C  CH3
CH3  C H  CH 2CH3 |
CH3
n-Pentane Isopentane Neopentane
B.P. = 309 K B.P. = 301 K B.P. = 282.5 K
The explanation for these effects lies in the vander waals forces. With unbranched alkanes, as molecular
weight increases, so does molecular surface areas. With increasing surface area, the van der Waals forces
between molecules increase, therefore more energy is required to separate molecule from one another.
Branching in the chain, on the other hand, makes a molecule more compact, reducing its surface area. As a
result, the strength of the van der waals forces operating between the molecules decreases. This results in
the lowering the boiling point.(Observe the boiling points of isomericpentanes above)
3. Melting point : The melting points of alkanes do not follow a very smooth gradation with the increase of
molecular size. Alkanes with even number of carbon atoms have higher melting point than the next lower and
next higher alkanes having odd number of carbon atoms.

It is explained by the fact that alkanes with an odd number of carbon atoms have their end-carbon atoms on
the same side of the molecule and the even numbered carbon atoms alkanes have their end-carbon atoms
on the opposite sides of the molecules. Thus, alkanes with even number of carbon atoms pack closely in
such a manner as to permit greater inter molecular attraction and therefore have slightly higher melting point.
The more compact molecule, the more is the packing efficiency of a molecular solid. This results in higher
melting point. For example, neopentane when packed (in solid form) has a higher melting point as com-
pared to n-pentane (less effective packing due to open chain structure).
Name Formula B.P. (K) M.P. (K) Density
(as liquids)
Methane CH4 111.0 90.5 0.4240
Ethane CH3CH4 184.4 101.0 0.5462
Propane CH3CH2CH3 230.9 85.3 0.5824
n-Butane CH3(CH3)2CH3 272.4 134.6 0.5788
Isobutane  CH3 2 CH  CH3 261.0 114.7 -
n-Pentane CH3(CH2)3CH3 309.1 143.3 0.6264
Isopentane  CH3 2 CH  CH 2  CH 3 300.9 113.1 -
Neopentane  CH 3 3 C  CH3 282.5 256.4 -

3. Solubility : ‘Like dissolves like’ is the general rule of solubility. In the light of this rule, alkanes which are
predominantly non-polar are insoluble in polar solvents such as water, alcohol, etc. but are highly soluble in
non-polar solvents such as Petroleum either, Benzene, Carbon tetrachloride, etc.
4. Density : The density of alkanes increases with the increase in the molecular masses till the limiting value
of about 0.8 g cm3 is reached. This means that all alkanes are lighter than water.
Reaction of Alkanes :
Alkanes being saturated compounds undergo only substitution reactions, at C  H bond. The hydrogen atom is
replaced by other atom(s) such as : X-(halogens), NO2 (nitro), etc.
1. Halogenation :
Replacement of H-atom by X-atom (X = Cl, Br, I) in presence of UV light. The substitution reaction is
explained by free radical mechanism.
2 Cl /h 2 Cl / h
2  CHCl 
2 Cl / h Cl / h
CH 4  CH3Cl  CH 2Cl2  3  CCl4
The bromination is same as chlorination but it is relatively slow and high temperature favours it.
The iodination is reversible reaction :  CH3I + HI
CH4 + I2 
Note : HI is a reducing agent, so oxidising agents, such as HIO3, HNO3, HgO are used to oxidise HI.
5HI + HIO3 
 3H2O + 3 I2
Fluorination of alkanes is too vigorous to be controlled under ordinary conditions. Further-more, fluorina-
tion brings about extensive rupture of C  C and C  H bonds leading to a mixture of product. Alkyl
fluorides are more conveniently prepared indirectly by heating suitable chloroalkanes with inorganic fluo-
rides such as AsF3, SbF3, AgF, HgF2 etc. For example,
2 CH3CH 2 – Cl + Hg2F2 
 2 CH3CH2 – F + HgCl2
The above reaction is known as Swarts reaction.
Ease of halogenation : 3 H > 2H > 1H > CH4

Reactivity of X2 : F2 > Cl2 > Br2 > I2
The reactivity decreases with the electronegativity of the halogens.

Consider halogenation in Isobutane.

Cl
Cl2 , h
|
CH3  C H  CH3   CH3  C H  CH 2Cl  CH3  C  CH3
| 25 C | |
CH3 CH 3 CH3
(63%) (37%)
Br
Br2
|
CH3  C H  CH3   CH3  C CH 3
127C
| |
CH3 CH3
(99%)
The above reactions show that Bromine is less reactive toward alkanes (in general) than chlorine. But
bromine shows greater ability to identify among different types of hydrogen atom (i.e., primary, secondary
and tertiary). It gives exclusive replacement of tertiary hydrogen atom. Chlorine, on the other hand is less
selective than Bromine. Fluorine is even less selective than Chlorine and gives equal percentage of substituted
products. (We will discuss mechanism of this reaction later)
Note :  Laboratory chlorination of alkanes is often done with SO2Cl2 (sulphuryl chloride), instead of Cl2 and an
organic perioxide, ROOR is used as an indicator.
 During monchlorination, number of monochlorinated products formed are equal to number of different
types of hydrogen atoms in the alkane.
2. Nitration :
Lower members do not react with conc. HNO3 at ordinary temperatures but long chain members on
heating with HNO3 yield nitro-alkanes.
400C
C6H13  H  HONO2  C6H13 NO 2  H 2O
(vapour)
However, when a mixture of vapour of an alkane and nitric acid is heated at 400 - 450°C, nitroalkane is
formed readily. By this process lower as well as higher alkanes can be converted into nitroalkanes.
450C
CH 3  H  HONO 2  CH3 NO2  H 2O

(vapour)
In alkanes having two or more carbon atoms, there is always a possibility that the C - C bonds may break
at high temperature and a mixture of nitro alkanes is formed.
HNO
3  CH CH CH NO  CH  C H  CH  CH CH NO  CH NO
CH 3CH 2CH3  3 2 2 2 3 3 3 2 2 3 2
400 C |
NO2

3. Sulphonation :
Lower alkanes do not undergo sulphonation but higher member (from hexane onwards) are sulphonated
slowly when treated with fuming sulphuric acid at about 400°C.
SO
3
C6H13  H  HOSO3H  C6H13SO3H  H 2O
Hexane sulphonic acid
However lower members such as Propane, Butane, Pentane, etc., react with SO3 in vapour phase to form
Sulphonic acids.
4. Cracking : (Pyrolysis)
The decomposition of a compound by heat is called pyrolysis. The alkanes, on heating under high tempera-
ture in absence of air, are broken down into lower alkanes, alkenes and hydrogen during cracking of
alkanes,either rupture of carbon-hydrogen bonds or rupture of carbon-carbon bonds take place resulting in
the formation of mixture of lower alkanes, alkenes and hydrogen. The rupture of C – H bonds is catalysed
by oxide of Chromium, Vandium, Molybednum, etc., and the rupture of C – C bonds is catalysed by Silica,
Alumina, Zinc oxide, etc.
500C
C2 H 6   CH 2  CH 2  H 2
Cr O2 3
500C
C3H8   CH3CH  CH 2  H 2
Cr O 2 3
500C
C3H8   CH 2  CH 2  CH 4
Al2 O3
5. Reaction with Steam :

Ni
CH 4  H 2O   CO  3H 2
1273 K
6. Combustion :
(a) Complete Combustion :
CH4 + 2O2 
 CO2 + 2H2O
3n  1 
CnH2n + 2 +   nCO2 + (n + 1) H2O + heat
 O 2 
 2 
Note : Enthalpy of combustion increases with increase in number of carbon atoms in alkane. For isomeric alkane,
enthalpy of combustion decreases with increase in branching

(b) Incomplete Combustion : If the combustion of alkanes is carried out in limited supply of air or
oxygen, CO is produced along with unburnt carbon in the form of carbon black or soot.
2CH4  3O2 
 2CO  4 H2O
(limited)
CH 4  O 2 
 C  H 2O
(limited) Carbonblack
Carbon black is used in the preparation of black inks, paints, polishes etc.
(c) Catalyst Oxidation : Different prodcuts are formed under different conditions.
(i) When a mixture of methane and oxygen (9 : 1 by volume) at a pressure of 100 atm. is passed
through a copper tube at 573 K, methanol is formed.
100 atm. 573 K
2 CH 4  O2 
 2 CH3OH
Cu tube
Methane Methanol
(ii) When a mixture of methane and oxygen under pressure is passed over heated molybdenum
oxide, it is oxidised to methanal.
Mo O
2 3  HCHO  H O
CH 4  O2  2
 , pressure
Methane Methanal
(iii) Higher alkanes on oxidation in presence of silver oxide give carboxylic acids.
2 Ag O
2 R  CH3  3O 2  2 RCOOH  2 H 2O

Alkane Carboxylic acid
(iv) In presence of oxidising agents such as KMnO4, K2Cr2O7 etc.
CH3 CH3
| |
alk .
CH 3  C  H  (O)  CH3  C  OH
KMnO4
| |
CH3 CH3
Isobutane tert-Butyl alcohol
7. Aromatisation :
Cr O  Al O
2 3 2 3  C H (Benzene)  4 H
CH3   CH 2  4  CH3 
 6 6 2
600 C /15atm

8. Isomerization :
When n-alkanes are heated with anhydrous aluminium chloride and hydrogen chloride at 573 K under a
pressure of about 35 atm, they are converted into branched chain alkanes. For example,
CH 3
AlCl3 / HCl
|
(i) CH3CH 2CH 2CH3   CH3  C H  CH3
573K
Isobutane
CH3 CH3
AlCl3 / HCl
| |
(ii) CH 3  (CH 2 )4  CH3   CH 3  C H  CH 2CH 2CH3  CH3CH 2  C H  CH 2CH3

n - Hexane 2 - Methylpentane 3 - Methylpentane
Illustration - 1 Identify A, B, C, D.
SOLUTION :
NOW ATTEMPT IN-CHAPTER EXERCISE-A BEFORE PROCEEDING AHEAD IN THIS EBOOK

ALKENES : [CnH2n] Section - 2
Alkenes form a homologous series, represented by a general formula : CnH2n. These have one C=C bond
or one can say that two carbon atoms (adjacent) in alkenes show sp2 type of hybridisation. The important
members of alkenes are: Ethene (CH2 = CH2), Propene (CH3 CH = CH2), 1-Butene (CH3CH2CH = CH3)
and its isomers, 2-Butene (CH3CH = CHCH3) and Iso-butene  CH3  C  CH 2  .
 | 
 CH 
 3 
Generally, alkenes are also represented as :
1. Terminal alkenes RCH = CH2, R2C = CH2
2. Non-terminal alkenes RCH = CHR, R2C = CHR, R2C = CR2 (where R : alkyl radical)
Preparation of Alkenes :
1. Dehydration of Alcohols :
The dehydration of alcohols is generally carried out in either of two ways :
(a) Heating the alcohol with conc. H2SO4 or H3PO3 to temperature as high as 170°C.
(b) Passing the vapours of alcohol over alumina (Al2O3) at 350 – 400°C.
RCH2CH2OH 
 RCH = CH2 (alkene) + H2O
Ease of dehydration is 3° alcohol > 2° alcohol > 1° alcohol.

Dehydration is governed by Saytzeff or Zaitsev rule i.e., the greater is number of alkyl groups attached to
doubly bonded ‘C’ atoms, the more stable is the alkene.
conc. H SO
2 4  CH CH  CHCH  CH CH CH  CH
CH 3CH 2  C H  CH3  3 3 3 2 2
| T 170C (80%) (20%)
OH
Order of Stability : R2C = CR2 > R2C = CHR > R2C = CH2 > RCH = CHR > RCH
= CH2 > CH2 = CH2
Note : If there are two geometric isomers, i.e., cis and trans isomers, then it is the trans isomer which is more
stable than the cis one.

2. Dehydrohalogenation of Alkyl Halides :

alc. KOH, 
CH3CH2CH 2 Br  CH3CH  CH 2
alc. KOH, 
CH 3CH 2  C H  CH3 
 CH3  CH  CH  CH3  CH 3  CH 2  CH  CH 2
| 2-Butene 1-Butene
Br (major) (minor)
Saytezeff prodcut Hoffmann product
The formation of less substituted alkene in an elimination reaction is called as a Hoffmann Elimination and
that of more substituted alkene as a Zaitsev Elimination or Saytzeff’s elimination.
Ease of dehydrohalogenation is in the order : 3° alkyl halide > 2° alkyl halide > 1° alkyl halide.
Ease of dehydrohalogenation for different halogens is in the order : Iodine > Bromine > Chlorine.
We can also used alkoxide ion, RO  , which acts as a strong base. The alkoxide ion abstracts a proton from
  carbon . Then dehydrohalogenation is known as   elimination or 1, 2  elimination.
CH3 CH3
| |
EtO
 CH3  C  EtOH  Br 
CH3  C  Br 
| Ethoxide ||
CH3 CH 2
Note : (i) In case of 1 RX, alkoxide (R’ O  ) does nucleophilic substitution of form ethers [R' O R].
(ii) By using alc. KOH [ KOH / ROH ], 1, 2,3 alkyl halides give elimination products.
3. By dehalogenation of Viccinal Halides :
CH 2BrCH 2Br  Zn 
 CH2  CH2  ZnBr2
4. Electrolysis of aqueous solution of sodium salts of dicarboxylic acids : (only for Ethene)
5. Cracking of Alkanes :
500C
C2 H 6  C2 H 4  H 2
Cr2 O3

500C
CH3CH 2CH3  CH3CH  CH 2  H 2
Cr2O3
6. Partial Hydrogenation of Alkynes :

The hydrogenation of alkynes to an alkene is brought about by the use of special catalysts. This is an
example of “Stereospecific reaction’’.
Note : Reaction that produce a particular stereoismers of the product is called as steroselective reaction.
(a) Using Lindlar catalyst (Pd/CaCO3 or Pd/BaSO4) in quinoline to give a cis alkene.
This is also called as syn addition, as two H-atoms are added to the same side.
This reaction can also be achieved by using Ni2B (called as P - 2 catalyst)
(b) Using Lithium (or Sodium) in NH3 (or in ethyl amine) at low temperature, gives trans alkene.
This is also called as anti addition, as two H-atoms are added to the opposite side of the bond.
Stability of Alkenes :
The reactivity of different types of alkenes in decreasing order is as follows : (As per heat of hydorgenation)
CH 2  CH 2  R  CH  CH 2  R  CH  CH  R  R 2 C  CH 2  R 2 C  CHR  R 2 C  CR 2
The heat of hydrogenation is always exothermic and experimentally it has been found that :

1
Stability of alkene  (i.e., higher is the heat of hydrogenation, higher is
Heat of hydrogenation reactivity and lower is the stability of an alkene)
Thus stability of alkenes in decreasing order is as follows :
R 2 C  CR 2  R 2 C  CHR  R 2 C  CH 2  RCH  CHR  RCH  CH 2  CH 2  CH 2

trans > cis
Physical Properties of Alkenes :

1. Physical state and smell : The first three members of the family, i.e., Ethene, Propene and Butene
are colourless gases. The next eleven members (C5  C15) are liquids while the higher ones are solids.
Except Ethene which has a pleasant smell, all other alkenes are odourless.
2. Melting points : The melting points of alkenes do not show regular gradation. However, the melting
points of alkenes are higher than those of the corresponding alkenes.
Amongst isomer of alkenes, trans-alkenes have higher melting points than their corresponding cis-
isomers.
3. Boiling points : The boiling points of alkenes, like alkanes, show a regular gradation with the increase
in the number of carbon atoms. Amongst the alkenes which show geometrical isomerism, cis-alkenes
have higher boiling points than the corresponding trans-isomers. This is due to the reason that cis-
alkenes being polar have stronger dipole-dipole interactions while trans-alkenes being non-polar (or
weakly polar) have weak induced dipole interactions.
4. Solubility : Alkenes like alkanes being either non-polar or weakly polar molecules are practically
insoluble in water and other polar solvents but are quite soluble in non-polar solvents such as benzene,
CCl4, petroleum ether, etc. and weakly polar solvents such as ether.
5. Density : The densities of alkenes, like those of alkanes, increase with the increase in molecular mass
till they have a limiting value of 0.89 g cm3. Thus, all alkenes are lighter than water.
Compound M.P. (°C) B.P. (°C) Density (g/mL)

Ethene –169 –104 0.384
Propene –185 –47 0.514
1-Butene - –6.3 0.595
cis-2-Butene –139 3.7 0.621
trans-2-Butene –106 0.9 0.604
1-Pentene –165 30 0.641
2-Methyl-1-butene –138 31 0.650

Reaction of Alkenes :
Alkenes undergo mainly addition reactions.
An addition that puts the part of AB on the same face of the reactant is called as syn addition.
The opposite of syn-addition is an anti-addition. An anti-addition puts the parts of AB on opposite faces
of reactants.
The addition reaction of alkenes are usually electrophilic addition.
Electrophile (E+) : An electron loving species looking for electron rich regions such as localised
pi   electron in alkenes and lakynees. Important Electrophiles :
H  , CI  , Br  , CH 3 etc.
Nucleophile (Nu) : A nucleus loving (electron rich) species looking to attack the electrophilic sites.
Important Nucleophiles : X  , OH  , OR  , CH 3 etc.

1. Addition of hydrogen halides (HX) :
The addition of HX to alkene is an electrophilic addition reaction. The reactivity order follows : HI > HBr
> HCl. The addition follows Markonikov’s rule. It states that in the addition of HX to an alkene, the
hydrogen atom adds to the carbon atom of the double bond that has the greater number of hydrogen atoms,
or the negative part of reagent adds to carbon having less number of hydrogen. The following examples
illustrate Markonikov’s addition.
(a) CH 2  CH  CH3  HI 
 CH3  C H  CH3  CH 3  CH 2  CH 2 I
|
I
2 - Iodopropane  Major  1 - Iodopropane  Minor 
(b) When 2-Methylpropene reacts with HI, the major product is tert. butyl iodide.
CH3 CH3
| |
CH3  C  C   HI 
 CH3  C  C   CH3  C H  C  I
| |
CH3 I
Major Minor
Anti Markonikov’s addition : When addition of HBr takes place in presence of perioxides (ROO
R or benzoyl peroxide), addition occurs in an anti-markonikov’s manner, i.e., Br is added to the carbon
having large number of H-atom.
ROOR
CH 3CH  CH 2  HBr 
 CH3CH 2CH 2Br
In presence of peroxides, free radical addition occurs in an anti-Markonikov’s fashion unlike the electrophillic
addition in above case (i.e., Markonikov’s addition).
Note : (i) Addition of HX in cycloalkenes also follows Markonikov’s addition.
(ii) Addition of HCl and HI in presence of perioxide follows Markonikov’s rule.

2. Addition of H2O :
The acid catalysed addition of H2O produces alcohols and follows Markonikov’s addition. The acids used
to catalyse the reaction are H2SO4 or H3PO4 (phosphoric acid).
CH3 CH 3
|  |
H
CH 3  C  CH 2  H 2O   CH 3  C  CH3
25C
|
OH
Isobutene tert. butyl alcohol
3. Addition of H2SO4 (cold and concentrated) :

Alkene react with cold concentrated H2SO4 to give alkyl hydrogen sulphates following Markonikov’s addi-
tion.
CH3  CH  CH 2  H  OSO3H 
 CH3  C H  OSO3H
cold |
CH3
Note : Alkyl hydrogen sulphates when boiled with water give alcohols. It is an irreversible reaction.
H O
2 
CH3  C H  OSO3H  CH3  C H  OH
boil
| |
CH3 CH3
Isopropyl hydrogen sulphate Isopropyl alcohol
4. Addition of Halogens (Cl2, Br2, I2) :

Alkenes decolourises Bromine water (Br2 in CCl4) following addition of Br2 across double bond. This
serves as a test of unsaturation. It follows anti-addition.
Cl
|
Low temp
CH3  CH  CH 2  Cl2  H3C  C H  C H 2  anti addition 
 anti addition  |
Cl
Viccinal dichloride

Note : (i) The addition of Br2 to cycloalkenes also follows anti-addition.
(ii) The addition of halogens to alkene is an anti-addition and provides an illustration for a stereoselective
and stereospecific reaction. For example, cyclohexene gives trans-1, 2-Dibromocyclohexane
(geometric isomer) is an example of stereoselective reaction. Consider addition of Br2 to cis and
trans-2- Butenes, which is an example of stereospecific reaction as the reactant (2-Butene) also
shows stereochemistry).
Note : The details of reaction mechanisms of all the addition reactions will be discuss later in the Chapter “Organic
Concepts”.
The above reaction, it is visulised as follows and remember the nature of product(s) : (Refer to the next
page)

5. Addition of halogen in aqueous solution :

When halogens are added in presence of H2O / THF (tetrahydrofuran) or NBS (N-bromo succinimide),
halohydrins are formed.
OH
| | | |
THF
 C  C   X 2  H 2O    C C
Alkene |
X
Halohydrins
The above reaction follows Markovnikov’s rule. It is an anti-addition reaction.
Note : (i) The cycloalkenes also reacts with aqueous Br2 to give anti-addition products.
(ii) In case of unsymmetrical alkene, halogen is added to the carbon atom with greater number of H-
atom, (i.e., Markonikov’s addition).
OH
|
H 2O or THF
CH 3  C  CH 2  Br2  CH3  C C H 2
| | |
CH3 H 3C Br

6. Oxymercuration - Demercuration :
An important method of formation of alcohols from alkenes. It occurs in two steps.
(i) Alkenes react with mercuric acetate Hg (CH3COO)2 or represented as, Hg (OAc)2 in a mixture of
THF and water to give a mercury compound.
O O
| | || | | ||
THF/ H2 O
 C  C   H 2O  Hg(O  C  CH3 ) 2    C  C   CH3  C  OH
| |
OH Hg  OAc
This step is known as Oxymercuration.
(ii) The mercury compound is reduced to alcohol with sodium borohydride.
| | NaBH 4 , OH
 | |
C  C     C  C   Hg  CH3  COO
| | | |
HO Hg  OAc HO H
Alcohol
The above reaction occurs in accordance with Markonikov’s addition. The ‘H’ becomes attached
to the carbon atom of the double bond with greater number of hydrogen atom.
H H H H
| | 1. Hg  OAc  /THF, H 2O | |
R  C  C  H  2 R  C  C H

2. NaBH 4 , OH | |
OH H
2 alcohol
Note : Observe that in the final product, OH comes from H 2O and H comes from NaBH 4 / OH  .
7. Hydroboration - Oxidation :
Hydrocration-oxidation serves as an important method for synthesis of alcohol 1 & 2  . It can be repre-
sented as :

H
| | | | |
 C  C  H  B  H 
  C  C
| | | |
H B H
|
H
Alkene Boron hydride Organoborane
Note : (i) The addition of boron hydride is syn-addition.

It is generally carried out by BH3 (boron hydride) B2H6 (diborane) in THF.
3 BH / THF
3CH 2  CH 2 
 (C2 H5 )3 B
Triethyl borane
3 BH /THF 3 CH CH  CH
2  (n  Pr) BH 
3 2  (n  Pr) B CH CH  CH
CH 3CH  CH 2 
 (n  Pr) BH 2  2 3
(ii) In each addition, the boron atom becomes attached to the less substituted carbon atom of double
bond and H is transferred from boron atom to the other carbon atom of double bond. Thus it
follows Anti-Markonikoff’s addition.
The organoboranes formed are oxidised and hydrolysed to alcohols by the addition of hydrogen
peroxides in an aqueous base.
H O
2 2  3ROH + Na BO H O2 2  3PrOH + Na BO
R 3B  3 3 (n  Pr)3 B  3 3
NaOH,25° C NaOH, 25°C
Note that alcohol formed is a primary alcohol (unlike that in Markonikov’s addition)
Consisder hydrobration and oxidation in 1-Methyl cyclopentene. It show syn-addition and anti-Markonikov’s
addition of H2O to alkene.
Note : Observe that in the final product, OH comes from H 2O 2 / OH  and H comes from BH 3 .
Note : Compare the alcohols formed above with those formed by Oxymercuration-Demercuration.

8. Hydroxylation of alkenes (Oxidation by cold alkaline KMnO4) :

The hydroxylation of alkene is brought about by alkaline KMnO4 or osmium tetraoxide (OsO4) to give 1, 2-
diols (or glycols).
| | KMnO 4
| |
 C  C     C  C (Vicinal alcohols or glycols)
OH  , cold | |
OH OH
| | 1. OsO 4 , pyridine
| |
 C  C     C  C (Vicinal alcohols or glycols)
2. NaHSO3 / H 2O
| |
OH OH
It represents syn-addition.
1. OsO , pyridine
4
CH 3  CH  CH 2   CH3  C H  C H 2
2. NaHSO3 / H 2 O
| |
OH OH
1, 2 - Propanediol
Note : Osmium tetra oxide, OsO4 gives a better yield than KMnO4. The hydroxylation like addition of Br2 is also
stereospecific. Consider hydroxylation in cis and trans isomeric alkenes.

9. Hydrogenation :
The hydrogenation of alkenes is a syn-addition, carried out by many reagents such as :
Na in liquid NH3 and alcohol ; H2, PtO2/CH3COOH ; H2/Ni at 573 K ; H2/Pd-Carbon in ethanol.
| | H2
| |
 C  C    C  C 
Ni (573K) | |
H H
This reaction also follows syn-addition rule.sheel

Consider hydrogenation in 1, 2-Dimethyl cyclohexene.
10. Oxidation of Alkenes :

(a) Oxidation by hot. conc. KMnO4 :
It gives acids or ketones depending upon structure of alkenes. The terminal alkenes gives acids
(ketones) and CO2, whereas non-terminal alkenes gives mixture of acids and ketones.
(O)
CH2  CH2 
 2CO2  2 H2O (HCOOH formed is oxidised further)
O
CH3CH  CH 2 
 CH3COOH  CO 2  H 2O
O
R  CH  CH  R 
 RCOOH  R 'COOH

O
CH 3  C  CHCH 3 
 CH3  C  O  CH3COOH
| |
CH 3 CH3
Note : Observe that the dialkylated side of double bond gives corresponding ketone.
Oxidation of cycloalkenes leads to the ring opening and gives dicarboxylic acids or keto acids.
(b) By Ozone (ozonolysis) :
Consider the ozonolysis of cycloalkenes :

Note : In ozonolysis, observe that we are using Zn/H2O or Pb/H2O or (CH3)2S which reduces the nascent oxygen
(O) given by ozonide.This is referred to as Reductive Ozonolysis. If Zn/H2O is not used, the product
aldehyde is oxidised to acid.
11. Alkylation :
CH3 CH3 CH3 CH3
| H2 SO4
| | |
CH3  C  CH 2  H  C  CH3   CH3  C H  CH 2  C  CH3  CH3  C  C  CH3
| | 0 10 C | | | |
CH3 CH3 CH3 CH3 CH3 CH3
 mixture of higher alkanes is formed 
12. Addition of oxygen :
13. Subst it ut ion in alkenes : (Partial Oxidation)

High temp.
CH 2  CH  CH3  X 2   CH 2  CH  CH 2 X  HX
or Low conc. X 2
Here, halogen replaces one of the hydrogen atoms of the methyl group. These hydrogen are allylic hydrogen
atom and hence the substitution is called as allylic substitution.
400 C  500 C
CH 2  CH  CH3  Cl2   CH 2  CH  CH 2Cl  HCl
gas phase
Allyl Chloride
Propene undergoes allylic bromination when it is treated with N-bromo succinimide (NBS) in CCl4 in
presence of perioxides or light.
NBS/CCl
4  CH  CH  CH Br
CH 2  CH  CH3  2 2
in ROOR or light
Allyl bromide
The mechanism is free radical substitution initiated by Br° (bromide free radical) to give intermediate allyl
radical which is stable. Consider allylic substitution in cyclohexene using NBS in CCl4.

Another intersting aspect of this reaction is that it also occurs in alkyl benzens.
14. Polymerisation :
High Temp
(i) n(CH 2  CH 2 )   (CH 2  CH 2  )n (Polyethene)
High pressure
(ii) Polymerization of substituted ethenes : A number of polymers can be obtained by using

substituted ethenes as monomers in place of ethene. For example,
 CH 2  C H  Polymerisation  CH 2  C H  
n |    | 
 Cl   Cl 
   n
Chloroethene 
Polyvinyl chloride PVC 
 Vinyl chloride 
n |    | 
 C H   C H 
 6 5  6 5 n
Styrene Polystrene
n |    | 
 CN   CN n
 
Acrylontrile or Polyacrylontrile(PAN)
vinyl cyanide
Polymerisation
n  CF2  CF2  
  CF2  CF2  n
Tetrafluoroethene Polytetrafluoroethene
 PTFE, Teflon 
Polyvinyl chloride (PVC) is used for making plastic bottles, syringes, etc. Polyacrylontrile is used for making
Orlon and Acrilan fibres used for making clothes, carpets and blankets.

Illustration - 2 Compound A (C6H13Cl)on treatment with hot alcoholic potassium hydroxide gave a
mixture of two isomeric alkense B and C, having formula C6H12. The mixture of (B) and (C), on ozonolysis,
furnished four compounds :
(i) CH3CHO (ii) C2H5CHO (iii) CH3COCH3 (iv) (CH3)2CHCHO
What are the structures of A, B and C ?
SOLUTION :
3 O
Alkenes C6H12 (B and C)  mixture of products
Zn  H 2 O
Try to draw the structures of alkenes (working backwards in ozonolysis reaction). Note that while joining
the products, keep in mind that on combining two products the sum of carbon atom must be six.
On carefully examining the products, alkenes B and C are :
3O
CH 3  C  CH  CH 2CH3  CH3COCH3  CH3CH 2CHO
|
CH3
O
3
and CH3  C H  CH  CH  CH3  (CH3 )2 CH  CHO  CH 3CHO
|
CH3
The structure of A must be :
alc.
CH3  C H  C H  CH2  CH3   CH3  C  CH  CH 2  CH3  CH3  C H  CH  CH  CH3
| | KOH,  | |
CH3 Cl CH3 CH3
(Major) (B) (Minor) (C)

Illustration - 3 Give the stucture of the major organic products form 3-Ethy-l-2-pentene form under
each of the following reaction conditions :
(A) HBr in the presence of peroxide (B) Br2/H2O (C) Hg(OAc)2/THF/H2O, NaBH4/OH–
SOLUTION :
Illustration - 4 A hydrocarbon X, C6H12 decolorizes bromine water and is oxidized to an acid Y by hot
acidic potassium permanganate solution. The acid Y can be resolved into two forms. Identify X and Y.
SOLUTION :
X is terminal alkene as it gives only Y.

Visualise the structure of Y (having a chiral centre) :
 O
 X is C2H5  C H  CH  CH 2 
 C2H5  CH  COOH Y
| |
CH3 CH3
Illustration - 5 Identify A, B, C, D. . . . .
SOLUTION :
Illustration - 6 Identify the products
SOLUTION :
Note that the dialkylated site in alkene give the same producer (Ketone) on oxidation and ozonolysis.
NOW ATTEMPT IN-CHAPTER EXERCISE-B BEFORE PROCEEDING AHEAD IN THIS EBOOK

ALKYNES : [CnH2n – 2] Section - 3
Alkynes form a homologous series, represented by a general formula : CnH2n – 2. These have one C  C
bond or one can say that two carbon atoms (adjacent) in alkynes show sp type of hybridisation. The
important members of alkynes are: Ethyne (CH  CH), Propyne (CH3C  CH), 1-Butyne (CH3CH2C 
CH) and its isomer, 2-Butyne (CH3C  CCH3).
Generally, alkynes are also represented as :
1. Terminal alkynes RC  CH
2. Non-terminal alkynes RC  CR, RC  CR (where R : alkyl radical)
Preparation of Alkynes :
1. Dehydrohalogenation of Dihalides : (Gem and Vicinal)
Br
2  CH BrCH Br  alc 2  CH  CH NaNH
CH 2  CH 2  2 2  CH 2  CHBr 
KOH, 
Viccinal dihalide
alc.
CH3 CH Br2 
 CH  CH
KOH, 
Gem dihalides
If alcoholic KOH to be used, vinylic halides are formed, as it is unable to remove vinylic hydrogen. So
NaNH 2 Sodamide) is used to produce alkynes.
2. Dehalogenation of Tetrahalides :
Br Br Br Br
| | | |
Zn
H  C  C  H  Zn 
 H  C  C  H  CH  CH
| |
Br Br
3. By dehalogenation of haloform :
Trihaloderivative of methane is knwon as haloform  CHX3  .
Chloroform and Iodoform on heating with silver powder undergo dehalogenation to form ethyne.
Trihaloalkane  R  CX3 on heating with silver powder also undergo dehalogentation to form symmetrical
internal alkyne.

4. Kolbe’s electrolytic reaction :

Acetylene can be prepared by electrolysis of a concentrated solution of sodium or potassium salt of Maleic
acid or Fumaric acid. Thus,
This reaction is called Kolbe’s electrolytic reaction.
Note : On electrolysis of aqueous solution of Potassium succinate, we get Ethylene (C2H4) as a product at anode.
5. From Graphite :
Electric arc
2C  s   H 2  g  

 CH  CH (Only acetylene can be formed)
1000 C
6. From calcium carbide :

CaC2 + 2H2O 
 C2H2 + Ca (OH)2 (Only acetylene can be formed)

Note : (i) Calcium carbide is formed as follows :

2000C
CaCO3 
 CaO  CO2

2500C
CaO  C 
 CaC2  CO 
(ii) Carbides of Na, K, Ca, Mg, Ba are considered to be ionic and give acetylene with H2O.
(iii) However, carbides of Cu and Ag are covalent and hence do not give acetylene with H2O.
7. Higher alkynes from Lower alkynes :
2 NaNH , liq. NH
3  CH  CNa  R 'X
CH  CH   CH  C  R ' (Terminal alkynes)
excess 1.0 eq.
NaNH 2 , liq. NH3 R 'X

CH  CH   Na  C  C  Na   R ' C  C  R ' (Non-terminal Alkynes)
2.0 eq. excess
2 NaNH , liq. NH RX
3  R  C  C  Na  
R  C  CH   R  C  C  R  (Non-terminal alkynes)
1.0 eq
Note : R’ can only be 1o and 2o alkyl or cycloalkyl groups only.
Physical Properties of Alkynes:
1. Physical state : The first three members of this family (Ethyne, Propyne and Butyne) are colourless
gases, the next eight are liquids while the higher ones are solids.
2. Smell : All the alkynes are odourless. However acetylene has garlic smell due to the presence of
phosphine as impurity.
3. Melting and boiling points : The boiling points and melting points of alkynes are slightly higher
than those of the corresponding alkenes and alkanes. This is probably due to the reason that
because of the presence of a triple bond, alkynes have linear structures and hence their molecules
can be more closely packed in the crystal lattice as compared to those of corresponding alkenes
and alkanes.
Hydrocarbon Ethane Ethene Ethyne

M.P. (K) 101 104 191
B.P. (K) 184.5 171 198

4. Solubility : Alkynes like alkanes and alkenes being non-polar are insoluble in water but readily
dissolve in organic solvents such as petroleum ether, benzene, carbon tetrachloride etc.
5. Density : Densities of alkynes increase as the molecular size increases. However, they are all
lighter than water since their densities lie in the range 0.69  0.77 g/cm3.
Reactions of Alkynes :
1. Electrophillic Addition Reactions :
YX X Y
|| | |
XY XY
C  C     C  C     C C
| |
X Y
(a) Addition of Hydrogen :
H
2  CH  CH 
2  CH  CH H
CH  CH  2 2 3 3
Pt /573K Pt /573K
Read hydrogenation of alkynes in the preparation of alkenes.
(b) Addition of Halogens : (X = Cl, Br, I)
Cl Cl
2Cl2
| | BaCl2 , 
CH  CH   H C CH   CCl 2  CHCl
solvent
| | Westrosol
Cl Cl
Westron
(c) Addition of Halogen acids : (HX)

HBr
CH  CH  HBr 
 CH 2  CHBr   CH3  CHBr2 (Markonikov’s rule )
(d) Addition of Hypohalous acids(HOX) :

Similarly,
(e) Addition of water (H2O) is presence of acid :
Note : The addition of water to alkynes also follows Markonikow’s rule. The hydrogen atom become attached to
the carbon atom with the greater number of hydrogen atoms. Therefore, when higher terminal alkynes are
hydrated, ketones, rather than aldehydes are formed.
However, if the unsymmetrical alkyne is nonterminal, a mixture of two isomeric ketones is obtained
in which the methyl ketone predominates. In case of benzene ring, phenyl ketones is major product .
O O
HgSO4 / H2 SO4
|| ||
 CH3CH 2  C  C  CH3   CH3CH 2CH 2  C  CH3  CH3CH 2  C  CH3CH3
333 K
2 - Pentanone (Major) 2 - Pentanone (Minor)
(f) Addition of HCN :

CH CHHCN 
 CH2 = CHCN (Vinyl cyanide also known as acrylonitrile)
Note : Acrylonitrile is used in manufacture of BuNa-S rubber and Orlon fibre.
(g) Addition of Acetic acid (CH3COOH) :

(h) Addition of Arsenic trichoride (AsCl3) :

CH CClAsCl2 
 ClHC = CHAsCl2
(Lewisite, a poisonous gas)
2. Nucleophillic Addition reactions :
CH  CH  Nu  
 H C  C H
|
Nu
(Vinylic carbanion)
Vinylic Carbanion is formed which is more stable than vinylic carbonium ion.
Addition of Methanol :
3 CH O  K 
HC  CH  CH3OH 
 CH 2  CH  OCH3
Acetylene 433  473 K Methyl vinyl ether
Methyl vinyl ether is used for making polyvinyl ether plastics.
3. Oxidative - Hydroboration
3 BH ,THF 2 2 H O ,OH 
  CH3  CH  CH  3 B 
CH 3  C  CH 
 CH3 
BH3 ,THF H 2 O 2 , OH 
CH3  C  C  CH3 
  |  B 
 CH  CH  C  
 3 3
4. Acetylide Formation :
AgNO
3  Ag  C  C  Ag
CH  CH 
ammonical
silver Acetylide, (white ppt.)

Note : This reaction shows the acidity of terminal alkynes and serves as a test for terminal alkynes.
CuCl
2 Cu  C  C  Cu
CH  CH 
amm.
Copper Acetylide (Red ppt.)
5. Oxidation of Alkynes :
(a) Oxidation in Neutral KMnO4 :
KMnO , H O
4 2  CH  C  C  CH
CH 3  C  C  CH3  2 (O)  3 3
298  303 K
But-2-yne || ||
O O
 Butan-2, 3-dione 
(b) Oxidation with cold dilute alkaline KMnO4 :
Alkynes are readily oxidised by cold dilute alkaline KMnO4 solution to give dicarbonyl compounds.
In case of terminal alkynes,  CH part is oxidised to – COOH group while in case of non-terminal
alkynes, CR part is oxidised to R  C  O group, For example :
|
O
1. NaOH, KMnO 4
||
CH 3  C  CH  3(O)   CH3  C  COOH
298  303 K
Propyne 2-Oxopropanoic acid
2. H

O O
NaOH, KMnO 4
|| ||
CH 3  C  C  CH 3   CH3  C  C  CH3
298 303 K
Acetylene, however, under these conditions gives oxalic acid probably due to further oxidation of
the initially formed glyoxal.
4 KMnO , NaOH  2(O)

HC  CH  2(O)  OHC  CHO 
 HOOC  COOH

Acetylene 298  303 K Glyoxal H Oxalic acid
During this reaction, the pink colour of the KMnO4 solution is discharged and a brown precipitate
of manganese dioxide is obtained. This reaction is, therefore, used as a test for unsaturation under
the name Baeyer’s test.
(c) Oxidation by acidic KMnO4 (hot) :

KMnO
4  R  COOH  R 'COOH
R  C  C  R ' 

H , heat
Not that it is similar to the oxidation of alkenes.

6. Ozonolysis :
(a) For non-terminal alkynes :
O O
1. O3
|| ||
R  C  C  R '   R  C  C R '
2. Zn, H2O
Note : If, Zn or Pb is not used, then the product is mixture of acids.

O O
O3
|| ||
R  C  C  R   R  C  OH  R   C  OH
mixture of acids
(b) For terminal alkynes :

3 O
H  C  CH  OHC  CHO
Zn / H 2 O
 Glyoxal 
O
O3
||
R  C  CH  R  C  CHO
Zn /H 2 O
   alkyl glyoxal 
7. Polymerization Reactions of Alkynes :

Like alkenes, alkynes also undergo polymerization reactions. For example,
(a) When acetylene is passed through red hot iron tube, it rimerises to give benzene.
(b) In presence of nickel cyanide as catalyst and under high pressure, four moelcules of acetyrene
combine to form a tetramer called cycloocta-1, 3, 5, 7-tetraene.
(c) However, in presence of CuCl/NH4Cl, acetylene first gives vinylacetylene and then divinylacetylene.
Thus,

CuCl/ NH Cl
4  H C  C  CH  CH  HC  CH
2 HC  CH  2  H 2C  CH  C  C  CH  CH 2
CuCl/ NH 4 Cl
Acetylene Vinylacetylene Divinylacetylene
Vinylacetylene is widely used in the manufacture of chloroprene which is the starting material for the
synthetic rubber neoprene.
Cl
|
Markonikov 's
CH 2  CH  C  CH  HCl   CH 2  CH  C  CH 2
addition
Vinylacetylene  one mole  across C  C Chloroprene
(d) Under suitable conditions, polymerization of acetylene produces the linear polymer polyacetylene.
It is a high molecular weight conjuated polyene containing the repeating unit (CH = CH  CH =
CH)n. Under proper conditions, this material conducts electricity. Since polyacetylenes have much
higher conductance than metal conductors, these can be used to prepare lighter and cheapter batteries.
Acidic character of Alkynes :

(a) Formation of alkali metal acetylides :
475C
 2HC  C Na   H2
2 HC  CH  2Na 
Ethylne Sodium acetylide
(Acetylene)
Liq. NH
R  C  CH 3
 NaNH 2  R  C  C  Na   NH3
196 K
(A terminalalkyne) (An acetylide)
During these reactions, the acetylenic hydrogen is removed as a proton to form stable carbanions (acetylide
ions). Sodium acetylide is decomposed by water regenerating acetylene. This shows that water is a stronger
acid than acetylene and thus displaces acetylene from sodium acetylide.
HC  C Na   H 2O 
 HC  CH  NaOH
Acetylene
(b) Formation of heavy metal acetylides :

CH  CH  2  Ag  NH3 2  OH  
 AgC  CAg  2 H 2O  4NH3
Ethylne Tollen's reagent Silver acetylide
(White ppt.)


R  C  CH   Ag  NH3  2  OH  
 R  C  C  Ag  H 2O  2NH3
Tollen's reagent Silver acetylide
(White ppt.)

HC  CH  2 Cu  NH3 2  OH  
 CuC  C  Cu  H 2O  4NH3
Ethyne Copper acetylide
(Red ppt.)
Unlike alkali metal acetylides, silver and copper acetylides are not decomposed by water. They
can, however, be decomposed with dilute mineral acids to regenerate the original alkynes.
AgC  CAg  2 HNO3 

 HC  CH  AgNO3
Silver acetylide Acetylene
CuC  CCu  2 HCl 

 HC  CH  2CuCl
Cooper acetylide Acetylene
(c) Formation of alkynyl Grignard reagents :

Dry
HC  CH  RMgX 
 HC  CMgX  RH
Acetylene Grignard reagent ether Acetylenic Alkane
Grignard reagent
Dry
R '  C  CH  RMgX 
 R '  C  CMgX  RH
Terminal alkyne ether Alkynyl
Grignard reagent
Illustration - 7 How would convert acetylene to acetone ?
SOLUTION :
HC  CH  CH3COCH3
In such question, try to visulaise formation of CH3COCH3 . It is formed by hydration of CH3C  CH.
So now convert HC  CH to CH3C  CH.
NaNH  CH Br
3  HC  C  CH 
2  HC  C  N a  2 H O/ H  / Hg 2
HC  CH  3  CH3COCH3
1.0 eq
 via Tautomerism 

Illustration - 8
Identify A, B, C . . . . . . . . .
1.NaNH
2 A 
2  B  H
3 C  D O
(a) Me  C  CH 
2.EtBr Pd  BaSO 4 Zn / H 2 O
quinoline
(b)
1. NaNH (2.0eqv.)
2 2, 2 4C H Liq.Li Br /CCl
(c) HC  CH  A 
 B 
2. EtBr (2.0eqv.) NH3
SOLUTION :
(a)
(b)
(c)
NOW ATTEMPT IN-CHAPTER EXERCISE-C BEFORE PROCEEDING AHEAD IN THIS EBOOK

CYCLOALKANES AND CYCLOALKENES Section - 4
These are closed chain hydrocarbons having CnH2n as general formula. These are isomeric to alkenes.
Cyclo propane or C3H6 or
Cyclo butane or C4H8 or
Cyclo pentane or C5H10 or
Cyclo hexane or C6H12 or
The bond angles in lower members, i.e., in cyclopropane and cyclobutane are quite different from normal
tetrahedral bond angle of 109.5°. Hence these are unstable as compared to higher member such as
cyclopentane and cyclohexane which have bond angles nearer to tetrahedral bond angles. The two small
cycloalkanes are said to have a ring strain due to bond deformation. This is referred to as Baeyer strain
theory. Due to this strain, cyclopropane and cyclobutane are highly reactive and tend to open their rings.
Cycloalkenes : These are isomeric to alkynes and alkadienes. Some important cycloalkenes are :
Cyclo propene or C3H4 or

Cyclo butene or C4H6 or
Cyclo pentene or C5H8 or
Cyclo hexene or C6H10 or
1-Methyl cyclopentene
1, 2-Dimethyl cyclohexene
Preparation of cycloalkanes and cycloalkenes :

1. Dehalogenation of iolated dibromides :
It is not a good method because of poor yield.
2. From diazomethane (CH2N2) :

Diazomethane or simple heating gives Carbene, : CH2, which adds to the double bond of alkenes to give
cyclopropane.

CH2 N2 
 : CH2  N 2

Note that the addition of : CH 2 (carbene) is sterospecific as 2-butene exist in cis and trans forms.
3. Simmon - Smith Reaction :

It is another method to form cyclopropane and its derivatives. Instead of diazomethane, di-iodomethane,
CH2I2 with Zn-Cu alloy in diethyl ether is used. The rest of the reaction is same as above.
4. Heating calcium/barium salts of dicarboxylic acids :

By heating barium salts of discarboxylic acids, cyclic ketones are formed, which on Clemmensen’s reduc-
tion (Zn-Hg/HCl) give cyclopentane, cyclohexanes and other higher derivatives.

5. Hydrogenation of benzene :
6. Diel - Alder Reaction :

It is an important reaction of conjugated dienes with double bonded compounds to form unsaturated cyclic
compounds. Let us take 1, 3Butadiene as conjugated diene and consider its reaction with some unsaturated
compounds such as Ethene and Vinyl alcohol. The unsaturated compounds are called as dienophiles. This
reaction proceed beacuse of formation of six membered cyclic transition state.
Note : (i)
‘G’ is preferably an electron withdrawing group (electronegative in nature) such as OH, NH2, 
CN, NO2, etc.
(ii) Each of the product can be hydrogenated to give a saturated compound.

Reaction of cycloalkanes :
1. Ring opening :
The ring of 5 carbons being stable does not open after reaction with hydrogen.
2. Chlorination :
3. Oxidation :
Note : Cyclobutane is opened in the presence of hydrogen and Ni. At ordinary temperatures, cyclobutanes resists
the action of halogens and hydrogen halides.
Reaction of Cycloalkenes :
The cycloalkenes show the reaction of alkenes. (Refer to the reaction of Alkenes). For a quick review of
the reactions, please go through the following page carefully. It shows all the typical reaction of alkenes
taking 1 - Methylcyclopentene as the substrate.


NOW ATTEMPT IN-CHAPTER EXERCISE-D BEFORE PROCEEDING AHEAD IN THIS EBOOK
ALKADIENES Section - 5
Alkadienes are isomers of alkynes and cycloalkenes. These are classified in three categories.
(a) Hydrocarbons containing cumulated double bonds are called allenes or cumulated dienes.
CH2 = C = CH2 Propadiene C3H4
CH2 = C = CHCH3 Butadiene C4H6
(b) Those dienes which have an alternate system of double and single bonds are called conjugated
dienes.
CH2 = CH–CH = CH2 1, 3 Butadiene
CH 2  C CH  CH 2
| 2-Methyl-1, 3-Butadiene
CH3
1, 3-Cyclohexadiene
(c) In case, when two or more sp3 hybridised carbon atoms come in between the double bonds in
dienes, then they are called isolated dienes.
CH2 = CH2– CH2 – CH2 = CH2 1, 4-Pentadiene
Note : Conjugated dienes are most stable among dienes. They are stabilised due to resonance.
Preparation of Conjugate dienes :

1. From isolated dihalides
NaNH
2  CH  CH  CH  CH
C H 2  CH 2  CH 2  C H 2  2 2
| |
Cl Cl 1, 3 - Butadiene
NaNH
2  CH  CH  CH  CH  CH  CH  CH  CH  CH  CH
CH 3  C H  CH 2  CH 2  C H 2  3 2 2 2 2
| |
Cl Cl 1, 3 - Pentadiene (Major) 1, 4 - Pentadiene (Minor)

2. From isolated diols :
H SO
2 4  CH  CH  CH  CH  CH  CH  C  CH
CH3  C H  CH 2  C H 2  2 2 3 2
| | T 170C
OH OH 1, 3 - Butadiene (Major) 1, 2 - Butadiene (Minor)
H SO
2 4  CH  CH  CH  CH  CH  CH  CH  CH  CH  CH
CH3  C H  CH 2  CH 2  C H 2  3 2 2 2 2
| | T 170C
OH OH 1, 3 - Pentadiene (Major) 1, 4 - Pentadiene (Minor)
Reactions of Conjugate Dienes :

For the discussion of reactions of conjugated dienes we shall take 1, 3-Butadiene as an example.
1. Electrophillic Addition :
1, 3-Butadiene when reacts with HCl show unusual behaviour to give mixture of two products :
3-Chloro-1-butene (1, 2-addition product) and 1-Chloro-2-butene (1, 4-addition product)
(a) The formation of 1, 4-addition product is interesting.
HCl
CH 2  CH  CH  CH 2 
 CH3  C H  CH  CH 2  CH3  CH  CH  CH 2Cl
25 C |
Cl
(1, 2 - addition) (1, 4 - addition)
Note : Usually 1, 4-addition product is major.
(b) Addition of HBr to 1, 3-Butadiene takes place differently at different temperatures to give 1, 2-
addition and 1, 4-addition products as follows :
CH2 = CH – CH = CH2 + HBr 

(i) At – 80°C (Low temperature) :
CH3  C H  CH  CH 2  CH3  CH  CH  CH 2 Br
|
Br
(1, 2 - addition)(80%) (1, 4 - addition) (20%)

(ii) A 40°C (Near room temperature and above) :
CH3  C H  CH  CH 2  CH3  CH  CH  CH 2 Br
|
Br
(1, 2 - addition)(20%) (1, 4 - addition) (80%)
Note : At high temperatures, in case of HBr, 1, 2-addition product rearranges to give 1, 4-addition product.
(c) Addition of Br2 to 1, 3Butadiene also gives a mixture of 1, 2-addition and 1, 4-addition products.
Br2
(i) CH 2  CH  CH  CH 2   C H 2  C H  CH  CH 2  C H 2  CH  CH  CH 2 Br
15C
| | |
Br Br Br
 1, 3 - Butadiene  (1, 2 -addition) (54%) (1,4 - addition) (46%)
2 Br
(ii) CH 2  CH  CH  CH 2  1, 4  addition is major
T  27 C
2. Free radical addition :

In presence of perioxides, both 1, 2-addition product and 1, 4-addition products are formed. Consider
addition of BrCCl3 in presence of perioxide.
 Cl3C  CH 2  C H  CH  CH 2  Cl3C  CH 2  CH  CH  CH 2 Br
CH2 = CH – CH = CH2 + BrCCl3 
|
Br
(1, 2 -addition) (1, 4 - addition)
Note : Temperature dependency of products is similar to that HBr addition. Also refer to Diel - Alder reactions
(diense with alkenes) in cycloalkenes.
3. Reduction :
Catalytic hydrogenation of conjugated dienes in presence of H2/ Li gives a mixture of 1, 2-addition and 1, 4-
addition product with the 1, 4-addition products being major.
H H H H
H 2 / Li
| | | |
CH 2  CH  CH  CH 2   CH 2  C H  CH  CH 2  CH 2  CH  CH  CH 2
Buta - 1,3 - diene But - 1 - ene (Minor) But - 2 - ene (Major)
However, the chemical reduction of 1, 3-Butadiene with sodium in alcohol gives mainly the 1, 4-addition
product, i.e., But-2-ene.

Na /alcohol
CH 2  CH  CH  CH 2 
 CH3  CH  CH  CH3
1, 3-Butadiene But-2-ene
Under these conditions the isolated double bonds are not reduced. This suggests that dienes are much more
reactive than simple alkenes.
4. Polymerization :
Peroxides
n  CH 2  CH  CH  CH 2    CH 2  CH  CH  CH 2   n
Buta-1, 3-diene Polybutadiene
Since each repeating unit in polybutadiene contains a double bond, it may have either cis or trans-configu-
ration. Actually the polybutadiene polymer obtained by free-radical polymerisation has trans-configura-
tion.
 CH3 
Peroxides
n |  
 CH  C CH  CH 
 2 2
2-Methylbuta-1, 3-diene
(Isoprene)
 Cl   Cl 
Peroxides
n  |    | 
 CH  C CH  CH   CH  C  CH  CH  
 2 2  2 2 n
2-Chlorobuta-1, 3-diene Polychloroprene
(Chloroprene) (Neoprene)
Neoprene is an important substitute for natural rubber and is superior to natural rubber in being
more resistant to oil, gasoline and other organic solvents.
50 Section
Section 55 Self Study Course for IITJEE with Online Support
Illustration - 9 Isomers A, B, C, and E have a common molecular formula C4H6. Identify A, B, C……as
per given instructions.
(a) A reacts with RMgBr to give a hydrocarbon.
(b) B reacts with Br2 to give a mixture of two products.
(c) C, an alicyclic compound, when oxidised by hot acidic KMnO4, gives a dicarboxylic acid whose
sodium salt on electrolysis gives an alkene, D. Also identify D.
(d) E is an alicyclic compound which is oxidized by hot KMnO4 to give 3-Oxo-1-butanoic acid.
SOLUTION :
C4H6 : can be alkyne, or alkadiene, or cycloalkene
(a) A should be terminal alkyne as it react with Grignard reagent.

 R MgBr
(A) CH3CH2C  CH  RH  CH3CH2C  C  MgBr
(b) B should be a conjugated diene as it gives a mixture of products.

Br
2  C H  C H  CH  CH  C H  CH  CH  C H
CH 2  CH  CH  CH 2  2 2 2 2
(B) | | | |
Br Br Br Br
(1, 2 - addition) (1, 4 - addition)
(c) D is clearly ethene as it is the only lakene

formed by Kolbe’s electrolysis.
(d)

Illustration - 10 Give the products.
(a) (b)
SOLUTION :
(a)
Note that aldehyde group is oxidised to acidic group
(b)
NOW ATTEMPT IN-CHAPTER EXERCISE-E BEFORE PROCEEDING AHEAD IN THIS EBOOK

AROMATIC HYDROCARBONS Section - 6
Benzene : [C6H6]
Structure :
Its molecular formula is C6H6. This implies unsaturation in benzene. It shows addition reactions : addition of
3 molecules of Hydrogen, 3 moles of Cl2 and 3 moles of Ozone (like alkenes).
This leads to idea of three double bonds. However, benzene fails to give unsaturation test (i.e., Baeyer’s test
or decolouration of bromine water). Benzene also gives substitution reactions like halogenation, nitration
etc. (like alkanes). On addition of H2, benzene forms cyclohexane (a cyclic hydrocarbon) C6H12. Kekule
(1865) proposed following structure the basis of the structure of cyclohexane. But this structure fails to
explain ozonolysis of Xylene [C6H4  (CH3)2], a derivative of benzene. So benzene is found to be a
resonance hybrid of two Kekule structures :
This is supported by ozonolysis of o-Xylene, which gives a mixture of Glyoxal, Methyl glyoxal, Dimethyl
glyoxal which can not be explained by either of Kekule structures.
Now benzene is considered as resonance hybrid of two Kekule structures. Resonance imparts stability to
the benzene due to delocalisation of  electrons over entire benzene ring . Since  electrons are not concen-
trated in any specific region, addtion reaction (electrophillic) are not common is benzene. However, in
benzene electrophillic substitution reactions are common as they are stabilized by resonance stabilisation of
intermediate Carbonium ion. When a group is introduced in benzene nucleus (ring), only one product
(monosubstitued) is obtained. On the other hand, when a group of electrophillic nature is introduced in a
mono-substituted benzene, three different isomers are possible.
In the above sequence, nature of X (group over mono-substituted benzene) is responsible for the formation
of either ‘m’ or ‘o’ & ‘p’ derivatives.

Directive (orienting) influence of groups :

(a) o and p directing groups : These groups direct the incoming group predominantly to the ‘o’ &
‘p’ position. Some important groups are :
 NH 2 ;  NHR ;  ;
 OH  ;
 OR  ;  R
X
All of these groups exerts +M effect over benzene and tends to increase electron-density over
benzene and make benzene strongly nucleophillic towards electrophiles. These groups are called
activating groups. -I effect (elctronegative or electron withdrawing nature) of these groups is weaker
as compared to +M effect. Halogens exerts +M effect over benzene but their -I effect is very
powerful. Though they are o and p directing (+ M effect) but are de-activating in nature and hence
it is difficult to carry out electrophillic substitution in halo benzenes. Alkyl group (R) are o and p
directing due to hyperconjugation (to be discussed later).
(b) m-directing groups : These groups direct the incoming groups predomintly to m-positions. Some
of the important groups are :
O OH R H
|| || | |
 C  OH ;  S  O ; C  O ;  C  O ;  NO 2 ;  CCl3
||
O
All m-directing groups, (except CCl3) either possess a positive charge or the key atom of substituents
has an electronegative atom linked by a multiple bond. The benzene nucleus containing these groups
undergo strong –M, –I, effect such that the displacement of electron takes place away from the
benzene ring. These groups tends to deactivate the benzene ring and hence makes it less nucleophillic
towards electrophiles.These are called as de-activating groups. Benzene having these groups will
have greater difficulty in electrophillic substitution reactions.
Preparation of Benzene :
1. Decarboxylation of Sodium Benzoate :
2. From Chlorobenzene :

3. From Phenol :
4. From Sulphonic Acid :
5. Synthesis :
Red hot Fe tube
3C2 H 2  C6 H 6
6. From Benzene Diazonium Chloride :
7. Manufacture :
(a) n-hexane :
2 3 Al O  Cr O
2 3
CH3  CH 2 4 CH3 
600C, pressure
This is known as Hydroforming or catalytic Reforming or aromatisation
(b) Coal Tar :
fraction
Dry distillation 
 COAL  TAR  Ligt  oil  fraction 

of wood Distillation 80  170C
Physical properties of Arenes :

1. Benzene and its homologues containing upto eight carbon atoms are colourless liquids with charac-
teristic smell.
2. Due to large hydrophobic hydrocarbon part, arenes are not soluble in water but are soluble in
organic solvents.
3. The melting points and boiling points of arenes increase with increase in the molecular size due to
a corresponding increase in the magnitude of van der Waal’s forces of attraction. Amongst isomeric
arenes, i.e., o-, m- and p-Xylenes, the p-isomer is most symmetrical, has the highest melting point.

Reaction of Benzene :
When benzene is treated with bromine in carbon tetrachloride in the dark or with aqueous potassium in the
dark or with aqueous potassium permanganate or with dilute acids, none of the expected reactions (addition
reactions) occurs. Benzene does add hydrogen in the presence of finely divided nickel, but only at high
temperature and under high pressures.
Benzene does react with bromine except in the presence of catalyst such as ferric bromide. The interesting
aspect of this reaction is that benzene show substitution not addition (like alkenes).
Substitution :
FeBr
3  C H Br  HBr
C6H 6  Br2  6 5
Addition : Benzene does not show addition reaction of Br2 or H2 at all under normal conditions.
When benzene reacts with bromine, only one monobromobenzene is formed. That is, only one compound
with the formula C6H6Br is found among the products. Similarly, when benzene is chlorinated, only one
monochlorobenzene results.
Two possible explanations can be given for these observations. The first is that only one of the six hydrogen
atoms in benzene is reactive toward these reagents. The second is that all six hydrogen atoms in benzene are
equivalent, and replacing any one of them with a substituent results in the same product. From the concept
of Resonance we know all six carbon atom form equivalent C – C and C – H bonds. Hence this is the
correct explanation.
Structure of Benzene
The fact that the bond angles of the carbon atoms in the benzene ring are all 120strongly suggests that the
carbon atoms are sp2 hybridized. If we accept this suggestion and construct a planar six-membered ring
from sp2 carbon atoms, a representation like and shown in figure emerges. In this model, each carbon is sp2
hybridized and has a p-orbital available for overlap with p-orbitals of its neighbouring carbons. If we con-
sider favaourble overlap of these p-orbitals all around the ring, the result is the model shown in figure.
(a) Six sp2-hybridized carbon atoms are joined in a ring (each carbon also bears a hydrogen atom).
Each carbon has a p-orbital with lobes above and below the plane of the ring. Fig.(1)
Fig. (1)
(b) Overlap of the p-orbitals forming pi() bonds around the ring results in the delocalisation of pi()
electrons on the ring. [Refer to Fig.(2), (3), (4)]

Fig. (2)
Fig. (3)
Fig. (4)
The six  electrons are thus delocalised and can move freely about the six carbon nuclei, instead of any two
as shown in figure (4). The delocalised  electron cloud is attracted more strongly by the nuclei of the
carbon atoms than the electron cloud localised between two carbon atoms. Therefore, presence of delocalised
 electrons in benzene makes it more stable than the hypothetical cyclohexatriene. X-Ray diffraction data
reveals that benzene is a planar molecule. It also indicates that all the six C – C bond lengths are of the same
order (139 pm) which is intermediate between C – C single bond (154 pm) and C – C double bond (133
pm). This absence of pure double bond in benzene accounts for the reluctance of benzene to show addition
reactions under normal conditions, thus explaining the unusual behaviour of benzene.
1. Addition of Hydrogen (H2) :

2. Ozonolysis :
3. Oxidation :
Benzene is unreactive towards even strong oxidising agents such as : KMnO4/K2Cr2O7. However
in drastic conditions, it can be oxidised slowly to CO2 and H2O. It can be burned (i.e., combustion)
to give luminous and smoky flame.
(a) Controlled oxidation with air :
Benzene on oxidation with air at 773 K in presence of V2O5 as catalyst gives Maleic anhy-
dride.
(b) Oxidation of alkyl benzene :
Note : If R is a 3alkyl group, then it resists oxidation the benzene ring is destroyed.
3. Substitution Reactions :
Most important reactions of benzene are electrophillic substitution reactions. These are also denoted as SE
reactions.

Elecrophiles :
  +
Cl+ (Chloronium ion), N O 2 (Nitronium ion), SO3 (Sulphur trioxide), R (Carbonium ion), R  C  O
(Acylium ion).
(a) Halogenation :
 FeCl4  Cl
FeCl3  Cl2 
Note : (i) In iodination, oxidising agents like HNO3 or HIO3 are used to oxidise HI, a reducing agent.
(ii) In presence of sunlight and absence of halogen carriers (i.e., AlCl3, FeBr3, etc), benzene adds three
molecules of chlorine to form Benzene hexachloride (BHC) or Gammexane.
h
C6 H 6  3Cl2 
 C6 H6 Cl6
It may be noted that this is an addition reaction, not a substitution reaction.
(b) Nitration :

 HSO 4  H O NO 2 
HNO3  H 2SO 4   NO2  H 2O
Base Acid |
(Nitrating mixture) H
(c) Sulphonation :
H 2S2O7 
 SO3 + H 2SO4
electrophile
(d) Introduction of alkyl and acyl groups in presence of Catalysts : AlCl3, FeCl3, SbCl3 (acting
as Lewis acids) or protonating agents like HF, H2SO4, H3PO4 etc. These are known as Friedal
Craft reactions.

(i) Alkylation :
 AlCl4 
RCl  AlCl3  R (alkyl carbonium)
Electrophile
Note : The above reaction can be achieved with :
(a) An alcohol in HF or dil H2SO4 (b) An alkenne in HF or dil. H 2SO 4 (at low temperature)
(a)
(b)
Obseve that 3 carbon is attached to the ring.

While during alkylation, we expect formation of polyalkylated products as alkyl groups are o- and p-directing and
activating
(ii) Acylation :
O
||
RCOCl  AlCl3 
 R C  AlCl4

Acylium ion is Electrophile

The above two reaction are called as Acctylation and Benzoylation respectively.
Some Friedal Craft acylation are shown below :
The above reaction is also known as Gatterman - Koch reaction.
Note : (i) Aryl and vinylic halides cannot be used in Friedal craft reactions as they do not form carbocations
easily.
(ii) In substituted benzenes, Friedal Craft reactions gives poor yield when electron withdrawing (de-
activating) groups are present on the ring. These include :
O
||
 NO 2 , CN  ,  COOH,  C  R,  CCl3 ,  SO3H
(iii) In Friedal craft alkylation. most stable carbocation (from alkyl halide or alkene) determines the final
substitution product.

It does not give npropyl benzene since CH3 – C HCH3 , being a 2° carbocation is more stable

than CH3CH 2CH 2 1  .
* The detailed mechanism of SE reaction will be discussed later in the chapter “Organic Concepts”.
(iv) Intramolecular Friedal Craft reactions of - & - alkyl alkanoic acid or alkanoyl chlorides give
cyclic products.
4. Dehydrogenation :
Toluene :
Preparation of Toluene :
1. Friedal craft alkylation :

2. From dialkyl cuprates :

 CH3 2 CuLi  C6 H 5I 
 C6H 5  CH 3  LiI  CH 3Cu
Reactions :
1. Oxidation :
(a)
(b)
This is also known as Etard reaction.
2. Substitution :
(a) Side chain substitution :

(b) CH3 group being o and p directing directs incoming electrophile to o and p position :
3. Addition Reactions :

Illustration - 11 One of the benzene ring of [4] phenylene undergoes catalytic hydrongation readily under
conditions usually used for ordinary alkenes, but the other benzene ring do not. Identify which of these two
reaction correctely represent product of hydrogenation of [4] phenylen ?
I.
II.
(A) Only I (B) Only II (C) Both I and II (D) None
SOLUTION
Reaction I correctly represent product of hydrogenation of [4]-phenylen beacuse of loss in anti-aromatic

characters of all four memebered rings.

Illustration - 12 Which is the major product of the following

intramolecular F.C. acylation reaction ?
SOLUTION
Enolic form is more stable than keto form due to more aromatic characters in enolic form.
NOW ATTEMPT IN-CHAPTER EXERCISE-F BEFORE PROCEEDING AHEAD IN THIS EBOOK

SUBJECTIVE SOLVED EXAMPLES
Example - 1
Give the structure of A, B and C (explanation are not required) :
(i) A (C4H8) which adds on HBr in the presence and in the absence of peroxide to give same product,
C4H9Br
(ii) B (C4H8) which when treated with H2O/H2SO4 gives C4H10O which cannot be resolved into optical
isomers.
(iii) C (C6H12), an optically active hydrocarbon which on catalytic hydrogenation gives an optically
inactive compound C6H14.
SOLUTION :
(i) A: CH3CH = CHCH3 symmetric alkenes give same product.
OH
H 2O
|
(ii) B: CH3  C  CH 2 
 CH 3  C  CH3 ; optically inactive (No chiral centre)
| H |
CH3 CH3
H H
| H 2 / Pt
|
(iii) C: CH3  C*  CH  CH 2 (active)   CH3  C  C2 H5
|  |
C 2H 5 C 2 H5
(* : Chiral centre)
optically inactive (No chiral centre)
Example - 2
An organic compound E (C5H8) on hydrogenation gives compound F (C5H12). Compound
E on ozonolysis gives formaldehyde and 2-ketopropanal. Deduce the structure of compound E.
SOLUTION : In such questions, by working backwards we join :
Note : Since 2-ketopropanal has two keto groups, hence there must be 2 moles of HCHO.
O
O3
||
(E)  2HCHO  CH3  C  CHO  E is :
Zn  H2 O
Self Study Course for IITJEE with Online Support Subjective Solved Example 67
Example - 3 The hydrocarbon, A adds one mole of hydrogen in the presence of a platium catalyst to
form neo-hexane. When A is oxidised vigorously with KMnO4, a single carboxylic acid, B is isolated. Give the
structures of A and B.
SOLUTION :
CH3
|
Hence A is : CH3  C  CH  CH 2
|
CH3
CH3
|
Clearly B is : CH3  C  COOH
|
CH3
Example - 4 What are product A, B and C in the following rection ?
2 H (O)

 A 
 B  C
Lindlarcatalyst
SOLUTION : Visualise the structure of given compound as follows :
Example - 5 Identify the products A, B and C and the reagent R in the following reactions :
alc. KOH 2 H O
(i) (CH 3 )2 C  CH 2CH 3  A (ii) HC  CH 
 2
B
| H / Hg
Cl
(iii) R
A 
BC
68 Subjective Solved Examples Self Study Course for IITJEE with Online Support
SOLUTION :
CH3 CH3
| RO |
(i) CH3  C  C HCH 3  CH3  C  CHCH3 (Saytzeff’s product)
| | (A)
Cl H
H O Tautomerises
2 

(ii) HC  CH   CH 2  CHOH 
 CH3CHO
 2
H / Hg
(B)
CH3
| R
(iii) CH 3  C  CHCH3  CH3CHO  (C)
R is clearly O3/Zn-H2O and (C) is acetone (CH3COCH3)

CH3
| O3
CH 3  C  CHCH 3   CH3CHO  (CH 3 )2 C  O
Zn /H 2 O
(A) (B) (C)
Example - 6 De-hydro-bromination of two compounds A and B gives the same compound C. C

regenerates A and B when reacts with HBr in the presence and absence of peroxide respectively. The hydrolysis
of A and B gives isomeric products D and E respectively. C when reacts with benzene in presence of H+ ions
gives 1, 1-Diphenylethane. Identify the compounds A to E.
SOLUTION : Visualizing the flow chart of the question as follows.
Recall Friedal Craft alkylation
 C is an alkene containing a – C = C – bond, hence C is vinyl benzene. C :
As per given reactions in question :
A: B: D: E:
Example - 7 An organic compound A, C5H9Br de-colourises bromine water and alk. KMnO4. It gives
B, C5H11Br when treated with H2, Pd-carbon in methanol. The reaction of A with NaNH2 gives C with the
evolution of NH3. C does not react with sodium but reacts with Lindlar catalyst to give D. It also reacts with
Na/liquid NH3 to give E. Both D and E are isomers. Identify the compounds A to E with proper reasoning.
SOLUTION :
Visualizing the flow chart of the question as follows :
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Hydrocarbons
Since D and E are isomers obtained by partial hydrogenation of ‘C’ (C : an alkyne) from two different
reagents, D and E must be geometric isomers with molecular formula C5H10. “Check this as follows”
NaNH 2
(A) C5H9 Br  C5H8  NH3  Br 
(Dehydrobro min ation)
2H
C(C5H8 )   C5H10 (D and E)
The alkene with molecular formula, C5H10 showing geometric isomerism is only 2-Pentene
[CH3CH = CHC2H5]
Hence the compound (C) is 2-Pentyne (Non-terminal alkynes do not react with Na).
A can be :
CH 3 C  CH  C 2 H5 or CH3CH  C  C 2H5
| |
Br Br
Both will give 2-Pentyne with NaNH2.

Accordingly B can be :
CH 3 C H  CH  C2 H5 or CH3CH 2  C HC 2 H5
| |
Br Br
NOW ATTEMPT OBJECTIVE WORKSHEET BEFORE PROCEEDING AHEAD IN THIS EBOOK
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This is known as Sabatatier-Sandern’s reaction.

Self Study Course for IITJEE with Online Support Section 1 1

2. From Alkyl Halides :

(b) Wurtz Reaction :

(c) Frankland Reaction :

4. Reduction of Aldehyde and Ketones :

5. From Carboxylic Acids :

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(c) Kolbe’s Electrolysis :

6. From Grignard Reagent ( Alkyl magnesium halides, RMgX) :

Note : Any copound having acidic H atom(s), decomposes Grignard reagent.

7. By action of water on Aluminium and Beryllium Carbide :

Note : Only Methane is formed by this reaction.

8. Through formation of Lithium Dialkycuprates :

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This is known as Corey House Synthesis

Note : (i) R can be 1°, 2°, 3° alkyl or aromatic group.

Physical Properties of Alkanes :

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Isobutane  CH3 2 CH  CH3 261.0 114.7 -

n-Pentane CH3(CH2)3CH3 309.1 143.3 0.6264

Isopentane  CH3 2 CH  CH 2  CH 3 300.9 113.1 -

Neopentane  CH 3 3 C  CH3 282.5 256.4 -

Self Study Course for IITJEE with Online Support Section 1 5

The above reaction is known as Swarts reaction.

Ease of halogenation : 3 H > 2H > 1H > CH4

The reactivity decreases with the electronegativity of the halogens.

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Self Study Course for IITJEE with Online Support Section 1 7

5. Reaction with Steam :

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(iv) In presence of oxidising agents such as KMnO4, K2Cr2O7 etc.

Self Study Course for IITJEE with Online Support Section 1 9

NOW ATTEMPT IN-CHAPTER EXERCISE-A BEFORE PROCEEDING AHEAD IN THIS EBOOK

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ALKENES : [CnH2n] Section - 2

Ease of dehydration is 3° alcohol > 2° alcohol > 1° alcohol.

Self Study Course for IITJEE with Online Support Section 2 11

2. Dehydrohalogenation of Alkyl Halides :

3. By dehalogenation of Viccinal Halides :

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6. Partial Hydrogenation of Alkynes :

This reaction can also be achieved by using Ni2B (called as P - 2 catalyst)

Self Study Course for IITJEE with Online Support Section 2 13

Thus stability of alkenes in decreasing order is as follows :

R 2 C  CR 2  R 2 C  CHR  R 2 C  CH 2  RCH  CHR  RCH  CH 2  CH 2  CH 2

Physical Properties of Alkenes :

Compound M.P. (°C) B.P. (°C) Density (g/mL)

14 Section 2 Self Study Course for IITJEE with Online Support

The addition reaction of alkenes are usually electrophilic addition.

Self Study Course for IITJEE with Online Support Section 2 15

1. Addition of hydrogen halides (HX) :

Note : (i) Addition of HX in cycloalkenes also follows Markonikov’s addition.

(ii) Addition of HCl and HI in presence of perioxide follows Markonikov’s rule.

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3. Addition of H2SO4 (cold and concentrated) :

4. Addition of Halogens (Cl2, Br2, I2) :

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Note : (i) The addition of Br2 to cycloalkenes also follows anti-addition.

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5. Addition of halogen in aqueous solution :

The above reaction follows Markovnikov’s rule. It is an anti-addition reaction.